CN103772615B - A kind of method improving polypropylene suspension graft acrylic acid percentage of grafting - Google Patents
A kind of method improving polypropylene suspension graft acrylic acid percentage of grafting Download PDFInfo
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Abstract
The invention discloses a kind of method improving polypropylene suspension graft acrylic acid percentage of grafting, the method is first by carrying out quenching pre-treatment to PP, reduce the degree of crystallinity of PP, grafts particle is formed nanometer level microporous in a large number simultaneously, then carry out graft reaction with olefin monomer in suspension.The monomer-grafted reaction efficiency of the present invention is high, and the percentage of grafting of graft product is high and can control.The method of raising polypropylene suspension graft acrylic acid percentage of grafting of the present invention, first pre-treatment is carried out to polypropylene, re-use Suspension Graft Method and carry out graft modification, pretreated method described in it is use the method for quenching process to carry out pre-treatment to polypropylene solution, allow polypropylene solution with the cooling of 100-120 DEG C/min speed, and obtain suspension after solid-liquid separation, preparation; Wherein said polypropylene solution is under agitation heated to 120-140 DEG C by polypropylene and solvent by 1:2-1:5 mass ratio and obtains.
Description
Technical field
The present invention relates to a kind of method of polypropylene suspension graft acrylic acid, more specifically to a kind of method improving polypropylene suspension graft acrylic acid percentage of grafting, belong to polymer chemistry and technical field of polymer.
Background technology
PP is the important a member in five large general-purpose plastics, because having excellent mechanical property, relative low price simultaneously, therefore development rapidly, its output and the production capacity trend still in steady-state growth, the new variety of PP emerge in an endless stream, except traditional PP plastics simultaneously, many high-crystallinities, the extraordinary PP of high melt flowability is also constantly expanding its use range.But PP molecular-chain polarr is low, with difficulties such as the high molecular alloying of polarity, bonding, printing, dyeing, limits it and apply further.In order to improve the polarity of PP, can meet the demand that plastics market increases fast to high value added product, domestic and international PP actively opens up new high-performance, multi-functional kind by the means of modification and compound.
PP method of modifying mainly contains copolymerization, blended, crosslinked and graft modification etc., and existing graft-modification method is mainly divided into fusion-grafting, solution graft copolymerization, solid phase grafting etc.Wherein fusion-grafting application is more extensive, but process of grafting is carried out in screw extrusion press, residence time of material is short, product graft rate is lower, temperature is more than PP melt temperature, and the grafted monomer that only suitable boiling point is higher and degraded is serious, comprises a large amount of unreacted monomer and initiator in product simultaneously, be difficult to remove, affect the use properties of product.Solution graft copolymerization temperature of reaction is lower, and side reaction is few, and palliating degradation degree is light, and products therefrom percentage of grafting is also higher, but a large amount of organic solvent of reaction needed consumption, and production cost is high, and postprocessing working procedures is complicated, and environmental influence is larger.Solid phase grafting utilizes interfacial agents to carry out swelling to PP particle surface, and grafted monomer and initiator carry out graft reaction by surperficial swell layer.The method temperature of reaction is lower, and solvent-free recovery problem, receives much concern, but the method graft reaction layer is shallow, reacts uneven, and in simultaneous reactions process, material easily coheres the group of connecing, and conduct heat uneven, product quality is wayward.In addition, the method is high to equipment requirements.
Occurred Suspension Graft method in recent years, it is low that this method provides a kind of energy consumption of reaction, and reaction conditions is gentle, and solvent load is few simultaneously, and product graft rate is higher, and product postprocessing is simple, the graft-modification method that production cost is low.But the document that the method is delivered is also few, and technology is not yet ripe.Publication number is that the patent of invention of CN1884326A adopts a kind of porous PP particle, and porosity 0.14-0.44 carries out Suspension Graft modification, carries out the graft polymerization of multiple olefin monomer in inorganic salt solution.The method mainly utilizes porous PP particle to have larger specific surface area, carries out graft polymerization reaction in solid-liquid interface, is thus difficult to obtain high percentage of grafting and stay-in-grade graft product.Publication number is that the patent of invention of CN1613887A employs dimethylbenzene and does to carry out swelling to the non-crystalline region of PP, and product graft rate is improved a lot.But Suspension Graft temperature of reaction, below the boiling point of water, directly cannot destroy the crystalline region of PP, and for the PP of high-crystallinity, non-crystalline region proportion is little, under the swelling action of interfacial agents, be difficult to the graft product obtaining high percentage of grafting.
The technical issues that need to address of the present invention are the Suspension Graft method of modifying for high-crystallinity PP, overcome the above-mentioned defect that prior art exists, provide a kind of and effectively can improve the method that degree of crystallinity PP carries out graft modification.
Summary of the invention
The present invention solves prior art and is inadequate, a kind of method improving polypropylene suspension graft acrylic acid percentage of grafting provided, the method is first by carrying out quenching pre-treatment to PP, reduce the degree of crystallinity of PP, grafts particle is formed nanometer level microporous in a large number simultaneously, then carry out graft reaction with olefin monomer in suspension.The monomer-grafted reaction efficiency of the present invention is high, and the percentage of grafting of graft product is high and can control.
The present invention is achieved through the following technical solutions:
The method of raising polypropylene suspension graft acrylic acid percentage of grafting of the present invention, first pre-treatment is carried out to polypropylene, re-use Suspension Graft Method and carry out graft modification, pretreated method described in it is use the method for quenching process to carry out pre-treatment to polypropylene solution, allow polypropylene solution with the cooling of 100-120 DEG C/min speed, and obtain suspension after solid-liquid separation, preparation; Wherein said polypropylene solution is under agitation heated to 120-140 DEG C by polypropylene and solvent by 1:2-1:5 mass ratio and obtains.
The method of raising polypropylene suspension graft acrylic acid percentage of grafting of the present invention, its further technical scheme is that described quenching process comprises the following steps:
The chilled brine of interior temperature≤-10 of chuck of quenching still DEG C is freezing, makes to generate mixture of ice and water, solid-liquid volume ratio >=50% of mixture of ice and water medium floe and water in quenching still;
Pour in quenching reactor by obtained polypropylene solution while hot, the cumulative volume of polypropylene solution and mixture of ice and water, than being 1:8-10, allowing polypropylene solution lower the temperature after 0 DEG C with 100-120 DEG C/min speed and carries out solid-liquid separation.Pretreated polypropylene material powders surface has a large amount of micropore (aperture 50-200nm), and diameier is 10-20 μm, and its degree of crystallinity can be reduced to about 50% (matching of WAXRD swarming) from 90%.
The method of raising polypropylene suspension graft acrylic acid percentage of grafting of the present invention, its further technical scheme be after described solid-liquid separation, wherein cold water, ice cube and small part solvent are back to quenching still; The Suspension Graft reactor preparation that after the mixture of another part solvent and water and pre-treatment, polypropylene material adds downstream after measuring by analysis obtains the suspension of Suspension Graft process, the interfacial agents that solvent reacts as Suspension Graft, water compositing dispersion medium.Further technical scheme is that described suspension is made up of pre-treatment polypropylene material, water and interfacial agents, and wherein pre-treatment polypropylene material and water press the preparation of 1:2-1:5 mass ratio, interfacial agents consumption be polypropylene material and quality and 5-10%.
The method of raising polypropylene suspension graft acrylic acid percentage of grafting of the present invention, its further technical scheme can also be described solvent is a kind of in diformazan Benzene and Toluene or both mixtures.
The method of raising polypropylene suspension graft acrylic acid percentage of grafting of the present invention, its further technical scheme can also be that described Suspension Graft Method carries out graft modification and comprises the following steps:
The suspension obtained after pre-treatment is added monomeric acrylic and initiator, stir be warming up to 40-120 DEG C of swells polypropylene 30min-120min, then at 80-120 DEG C of temperature graft reaction 3-5h, after filtration, drying obtains polypropylene-g-PAA graft product to product;
Or
The suspension agitation obtained after pre-treatment is warming up to 40-120 DEG C of swells polypropylene 30min-120min, adds monomeric acrylic and initiator, then at 80-120 DEG C of temperature graft reaction 3-5h, after filtration, drying obtains polypropylene-g-PAA graft product to product.Further technical scheme is the consumption of described Acrylic Acid Monomer is pre-treatment polypropylene quality of material 10-30%; Described initiator amount is pre-treatment polypropylene quality of material 0.2-0.6%.Described initiator is preferably dibenzoyl peroxide.
The invention has the beneficial effects as follows:
1, by the mode of quenching to PP pre-treatment, its degree of crystallinity can be reduced to about 50% (matching of WAXRD swarming) from more than 90%;
2, quenching pre-treatment forms a large amount of aperture on PP material powders surface is the micropore of 50-200nm, interfacial agents, reaction monomers and initiator can be allowed to enter oil phase, for graft reaction provides favourable condition in grafting process;
3, can use as interfacial agents the solvent used in PP preprocessing process, suspension is also recyclable, and environmental influence is little;
4, graft modification is carried out through suspension at a lower temperature through pretreated PP, can 13.0% be reached to the percentage of grafting of melt-blown PP, the AA monomer of high-crystallinity, its polarity is greatly improved, the requirement of different application occasion can be adapted to, as dyeing, absorption, anti-electrostatic etc.
5, PP graft modification uses Suspension Graft method of modifying, and temperature of reaction is lower, and energy consumption is little, and solvent usage quantity is few, and require low to production unit, procedure is simple.
Accompanying drawing explanation
Fig. 1. WAXRD spectrogram before and after PP pre-treatment in embodiment 1
In Fig. 1, the PP material non-crystalline region diffuse peaks area after quenching process increases, and more original PP degree of crystallinity reduces (to 50%).
The process flow diagram of Fig. 2 polypropylene suspension graft acrylic acid novel method
Embodiment
Below by way of specific embodiment, the present invention is described, but the present invention is not only limited to these embodiments.
Embodiment 1:
Melt-blown PP(MFR1300g/10min with high-crystallinity (90%)) for raw material, to prepare the preparation method of the melt-blown material of PP-g-AA as follows:
By melt-blown PP and xylene solvent in mass ratio 1:2 be under agitation heated to 140 DEG C, PP is dissolved completely; The xylene solution of PP is placed in the quenching still (PP solution and mixture of ice and water volume ratio are 1:8) got ready again and carries out quenching to 0 DEG C, product obtains pre-treatment PP material powders through suction filtration.By used xylene solution and water, separatory after leaving standstill reclaims.Pre-treatment PP material powders is weighed, and the xylene concentration detected in the mixture of water and solvent, according to its xylene content preparation Suspension Graft system, that is: PP and quality are than pressing 1:3, and dimethylbenzene makes the interfacial agents of suspension polymerization by 10% of PP and water total mass.N is passed in reactor
2as shielding gas, air in displacement still.Be heated with stirring to 90 DEG C of swelling 1h, again by 0.4% of initiator B PO(pre-treatment PP quality of material) be dissolved in AA monomer (10-30% of pre-treatment PP quality of material), add reactor, 3h is reacted at 90 DEG C, be cooled to room temperature, filter, products in water cleaning several times obtain PP-g-AA grafts.
The PP-g-AA graft product obtained, by its percentage of grafting of nonaqueous phase titration determination, uses fusion index instrument to measure its melt flow rate (MFR) (MFR), in table 1..From table 1., increase the consumption of grafted monomer, product graft rate can reach 12.7%, and its water contact angle is reduced to 60 ° from 105 °, the polarity of PP is greatly improved, can adapt to the requirement of different application occasion; Simultaneously, along with the raising of percentage of grafting, the MFR of product constantly declines, and this is because grafted chain PAA has the carboxyl of strong polarity, between molecular chain, form hydrogen bond, increase Intermolecular Forces, have impact on the motion of molecular chain, when monomer injected volume is 30% of PP quality, percentage of grafting 12.7%, MFR is 1336g/10min, has good flowing property while product polarity is improved.
Embodiment 2:
As follows with the preparation method that the melt-blown PP of high-crystallinity prepares the melt-blown material of PP-g-AA for raw material:
By melt-blown PP and dimethylbenzene in mass ratio 1:4 be under agitation heated to 140 DEG C, PP is dissolved completely; The xylene solution of PP is placed in the quenching still (PP solution and mixture of ice and water volume ratio are 1:8) got ready again and carries out quenching to 0 DEG C, product obtains pre-treatment PP material powders through suction filtration.By used xylene solution and water, separatory after leaving standstill reclaims.
Suspension Graft process is carried out graft polymerization according to embodiment 1 method and is obtained PP-g-AA grafts.
Get a certain amount of obtained PP-g-AA graft product by its percentage of grafting of nonaqueous phase titration determination; Fusion index instrument is used to measure its melt flow index (MFR), in table 2..Contrast table 1. and table 2. known, the consumption of solvent is increased when quenching process, reduce the concentration of PP in xylene solution, make when quenching, PP separates out the pre-treatment PP material obtained from solution less particle diameter and the porosity of Geng Gao, increases the specific surface area of material, thus in grafting process, interfacial agents dimethylbenzene enters PP internal batch more easily by hole, increases graft reaction interfacial area, improves percentage of grafting and the grafting efficiency of product.
Embodiment 3:
As follows with the preparation method that the melt-blown PP of high-crystallinity prepares the melt-blown material of PP-g-AA for raw material:
By melt-blown PP and dimethylbenzene in mass ratio 1:2 be under agitation heated to 140 DEG C, PP is dissolved completely; The xylene solution of PP is placed in the quenching still (PP solution and mixture of ice and water volume ratio are 1:8) got ready again and carries out quenching to 0 DEG C, product obtains pre-treatment PP material powders through suction filtration.By used xylene solution and water, separatory after leaving standstill reclaims.
Pre-treatment PP material powders is weighed, and the xylene concentration detected in the mixture of water and solvent, according to its xylene content preparation Suspension Graft system, that is: PP and quality are than pressing 1:3, initiator B PO presses 0.4% of PP quality of material, AA monomer presses the 10-30% of PP quality of material, and dimethylbenzene makes the interfacial agents of suspension polymerization by 10% of PP and water total mass.N is passed in reactor
2as shielding gas, air in displacement still.Be heated with stirring to 60 DEG C of swelling 1h, then react 3h at being warming up to 90 DEG C, be cooled to room temperature, filter, products in water cleaning several times obtain PP-g-AA grafts.
Pre-treatment PP material powders is added in reactor in PP and quality than the ratio of 1:3, supplement by total quality of material 10% and add dimethylbenzene as interfacial agents, by 0.4% of initiator B PO(PP quality) be dissolved in AA monomer (10-30% of PP quality), add reactor, and pass into N in reactor
2as shielding gas, and excluding air.Be heated with stirring to 60 DEG C of swelling 1h, then being warming up to 90 DEG C of reaction 3h, being cooled to room temperature, filtering and remove interfacial agents and dispersion agent, products therefrom water cleaning several times obtain PP-g-AA grafts.
Get a certain amount of obtained PP-g-AA graft product by its percentage of grafting of nonaqueous phase titration determination, use fusion index instrument to measure its melt flow rate (MFR) (MFR), in table 3..Contrast table 1. and table 3. known, by initiator and grafted monomer are once added before starting the reaction, first swelling at lesser temps 60 DEG C, then be warming up to 90 DEG C of temperature of reaction and carry out graft reaction, the step of adding monomer and initiator during the course can be reduced, simplify technique.
Comparative example:
As follows with the preparation method that the melt-blown PP of high-crystallinity prepares the melt-blown material of PP-g-AA for raw material:
Add in reactor in PP and quality than the ratio of 1:3 by original melt-blown PP, dimethylbenzene presses 10% of PP and water total mass as interfacial agents, and passes into N in reactor
2as shielding gas, and excluding air.Be heated with stirring to 90 DEG C of swelling 1h, then by 0.4% of initiator B PO(PP quality) be dissolved in AA monomer (10-30% of PP quality), add reactor, 3h is reacted at 90 DEG C, be cooled to room temperature, filter and remove interfacial agents and dispersion agent, products in water cleaning several times obtain PP-g-AA grafts.
Get a certain amount of obtained PP-g-AA graft product by its percentage of grafting of nonaqueous phase titration determination; Measurement result is in table 4.
Table 1.PP-g-AA(quenching process proportioning PP: dimethylbenzene=1:2, swelling temperature 90 DEG C)
| Case 1 | Case 2 | Case 3 | Original PP | |
| AA accounts for PP massfraction (%) | 10 | 20 | 30 | - |
| Product graft rate (%) | 4.4 | 9.0 | 12.7 | - |
| Monomer-grafted efficiency (%) | 46 | 49 | 48 | - |
| MFR（g/10min） | 1643 | 1598 | 1336 | 1300 |
Table 2.PP-g-AA(quenching process proportioning PP: dimethylbenzene=1:4, swelling temperature 90 DEG C)
| Case 1 | Case 2 | Case 3 | Original PP | |
| AA accounts for PP massfraction (%) | 10 | 20 | 30 | - |
| Product graft rate (%) | 6.5 | 11.4 | 13 | - |
| Monomer-grafted efficiency (%) | 70 | 64 | 50 | - |
| MFR（g/10min） | 1660 | 1378 | 1006 | 1300 |
Table 3.PP-g-AA(swelling temperature 60 DEG C, initiator and grafted monomer add before the reaction)
| Case 1 | Case 2 | Case 3 | Original PP | |
| AA accounts for PP massfraction (%) | 10 | 20 | 30 | - |
| Product graft rate (%) | 4.3 | 8.8 | 11.6 | - |
| Monomer-grafted efficiency (%) | 45 | 48 | 44 | - |
| MFR（g/10min） | 1659 | 1640 | 1445 | 1300 |
Table 4.PP-g-AA (original PP)
| Case 1 | Case 2 | Case 3 | |
| AA accounts for PP massfraction (%) | 10 | 20 | 30 |
| Product graft rate (%) | 1.1 | 1.8 | 2.1 |
| Monomer-grafted efficiency (%) | 11 | 9 | 7 |
The percentage of grafting measuring method of PP-g-AA grafts, and graft product melt flow rate (MFR) measuring method:
1, the percentage of grafting measuring method of PP-g-AA grafts
PP-g-AA is put into Soxhlet extractor acetone extraction 12h, extracting and separating unreacted monomer, residual initiator and homopolymer.
Taking a certain amount of purified PP-g-AA sample joins in dimethylbenzene, after heating makes it dissolving, add the ethanolic soln (0.05mol/L) of excessive NaOH, heating keeps solution boiling, condensing reflux 1h, to be cooled to room temperature, use thymolsulfonphthalein as indicator, with aqueous isopropanol (0.05mol/L) the back titration extremely yellow terminal of HCl.By following formulae discovery product graft rate:
G＝(N
1V
1-N
2V
2)×72×10
-3/mwt％
In formula: G---percentage of grafting (in every 100 grams of MODIFIED PP contained AA grams);
N
1---the concentration (mol/L) of NaOH-ethanolic soln;
V
1---the volume (mL) of NaOH-ethanolic soln;
N
2---the concentration (mol/L) of HCL-aqueous isopropanol;
V
2---the volume (mL) of HCL-aqueous isopropanol;
M---sample quality (g).
2, graft product MFR measuring method
Graft product melt flow rate (MFR) (MFR) measures according to ASTM1238 standard, with RL-Z1B1 melt flow rate (MFR) determinator at 230 DEG C, tests under 2.16kg load.
Claims (8)
1. one kind is improved the method for polypropylene suspension graft acrylic acid percentage of grafting, first pre-treatment is carried out to polypropylene, re-use Suspension Graft Method and carry out graft modification, it is characterized in that described pretreated method is use the method for quenching process to carry out pre-treatment to polypropylene solution, allow polypropylene solution with the cooling of 100-120 DEG C/min speed, and obtain suspension after being separated, preparing; Wherein said polypropylene solution is under agitation heated to 120-140 DEG C by polypropylene and solvent by 1:2-1:5 mass ratio and obtains.
2. the method for raising polypropylene suspension graft acrylic acid percentage of grafting according to claim 1, is characterized in that quenching process comprises the following steps:
The chilled brine of interior temperature≤-10 of chuck of quenching reactor DEG C is freezing, makes to generate mixture of ice and water, solid-liquid volume ratio >=50% of mixture of ice and water medium floe and water in quenching reactor;
Pour in quenching reactor by obtained polypropylene solution while hot, the cumulative volume of polypropylene solution and mixture of ice and water, than being 1:8-10, allowing polypropylene solution lower the temperature after 0 DEG C with 100-120 DEG C/min speed and carries out solid-liquid separation.
3. the method for raising polypropylene suspension graft acrylic acid percentage of grafting according to claim 2, after it is characterized in that described solid-liquid separation, wherein cold water, ice cube and small part solvent are back to quenching reactor; The Suspension Graft reactor preparation that after the mixture of another part solvent and water and pre-treatment, polypropylene material adds downstream after measuring by analysis obtains the suspension of Suspension Graft process, the interfacial agents that solvent reacts as Suspension Graft, water compositing dispersion medium.
4. the method for raising polypropylene suspension graft acrylic acid percentage of grafting according to claim 3, it is characterized in that described suspension is made up of pre-treatment polypropylene material, water and interfacial agents, wherein pre-treatment polypropylene material and water press the preparation of 1:2-1:5 mass ratio, interfacial agents consumption be polypropylene material and quality and 5-10%.
5. the method for the raising polypropylene suspension graft acrylic acid percentage of grafting according to claim 1,3 or 4, is characterized in that described solvent is a kind of in diformazan Benzene and Toluene or both mixtures.
6. the method for raising polypropylene suspension graft acrylic acid percentage of grafting according to claim 1, is characterized in that described Suspension Graft Method carries out graft modification and comprises the following steps:
The suspension obtained after pre-treatment is added monomeric acrylic and initiator, stir be warming up to 40-120 DEG C of swells polypropylene 30min-120min, then at 80-120 DEG C of temperature graft reaction 3-5h, after filtration, drying obtains polypropylene-g-PAA graft product to product;
Or
The suspension agitation obtained after pre-treatment is warming up to 40-120 DEG C of swells polypropylene 30min-120min, adds monomeric acrylic and initiator, then at 80-120 DEG C of temperature graft reaction 3-5h, after filtration, drying obtains polypropylene-g-PAA graft product to product.
7. the method for raising polypropylene suspension graft acrylic acid percentage of grafting according to claim 6, is characterized in that the consumption of described Acrylic Acid Monomer is pre-treatment polypropylene quality of material 10-30%; Described initiator amount is pre-treatment polypropylene quality of material 0.2-0.6%.
8. the method for the raising polypropylene suspension graft acrylic acid percentage of grafting according to claim 6 or 7, is characterized in that described initiator is dibenzoyl peroxide.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1613887A (en) * | 2003-11-06 | 2005-05-11 | 浙江工业大学 | Preparation of water phase suspended swelling graft polypropylene |
| CN1884326A (en) * | 2005-06-21 | 2006-12-27 | 北京化工大学 | Porous polypropylene particle suspension solid phase graft-modification method |
| CN102911316A (en) * | 2012-10-29 | 2013-02-06 | 哈尔滨工程大学 | Method for grafting polar monomer onto polypropylene through aqueous suspension solid-phase graft |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1613887A (en) * | 2003-11-06 | 2005-05-11 | 浙江工业大学 | Preparation of water phase suspended swelling graft polypropylene |
| CN1884326A (en) * | 2005-06-21 | 2006-12-27 | 北京化工大学 | Porous polypropylene particle suspension solid phase graft-modification method |
| CN102911316A (en) * | 2012-10-29 | 2013-02-06 | 哈尔滨工程大学 | Method for grafting polar monomer onto polypropylene through aqueous suspension solid-phase graft |
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